ES2625622T3 - Procedure for the manufacture of paper, cardboard and cardboard with high dry strength - Google Patents
Procedure for the manufacture of paper, cardboard and cardboard with high dry strength Download PDFInfo
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- ES2625622T3 ES2625622T3 ES07712497.2T ES07712497T ES2625622T3 ES 2625622 T3 ES2625622 T3 ES 2625622T3 ES 07712497 T ES07712497 T ES 07712497T ES 2625622 T3 ES2625622 T3 ES 2625622T3
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/18—Reinforcing agents
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/23—Lignins
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
- D21H17/43—Carboxyl groups or derivatives thereof
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Procedimiento para la fabricación de papel, cartulina y cartón con alta resistencia en seco, mediante la adición por separado de un polímero catiónico que contiene unidades de vinilamina y de un compuesto aniónico polimérico a un material de papel, eliminación del agua del material de papel y secado de los productos de papel, caracterizado porque se usa como compuesto aniónico polimérico (i) ácido lignosulfónico y/o un sulfonato de lignina y (ii) al menos un copolímero, el cual puede obtenerse mediante la copolimerización de (a) al menos una amida de ácido N-vinilcarboxílico de la fórmula significando en la misma R1, R2 >= H o alquilo de C1 a C6, (b) al menos un monómero monoetilénicamente insaturado que contiene grupos ácidos y/o sus sales de metal alcalino, de metal alcalinotérreo o de amonio y eventualmente (c) otros monómeros monoetilénicamente insaturados y eventualmente (d) compuestos, los cuales presentan al menos dos enlaces dobles etilénicamente insaturados en la molécula.Process for the manufacture of paper, cardboard and cardboard with high dry strength, by separately adding a cationic polymer containing vinylamine units and a polymeric anionic compound to a paper material, removing water from the paper material and drying of paper products, characterized in that the polymeric anionic compound used is (i) lignosulfonic acid and / or a lignin sulfonate and (ii) at least one copolymer, which can be obtained by copolymerizing (a) at least one N-vinylcarboxylic acid amide of the formula meaning R1, R2> = H or C1 to C6 alkyl, (b) at least one monoethylenically unsaturated monomer containing acid groups and / or their alkali metal salts, metal alkaline earth or ammonium and optionally (c) other monoethylenically unsaturated monomers and optionally (d) compounds, which have at least two ethylenically unsaturated double bonds in the molecule.
Description
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DESCRIPCIONDESCRIPTION
Procedimiento para la fabricacion de papel, cartulina y carton con alta resistencia en secoProcedure for the manufacture of paper, cardboard and cardboard with high dry strength
La invencion se refiere a un procedimiento para la produccion de papel, cartulina y carton con alta resistencia en seco, mediante la adicion por separado de un polfmero que comprende unidades de vinilamina y de un compuesto anionico polimerico a un material de papel, la eliminacion de agua del material de papel y el secado de los productos de papel.The invention relates to a process for the production of paper, cardboard and cardboard with high dry strength, by separately adding a polymer comprising vinylamine units and a polymeric anionic compound to a paper material, removing water from paper material and drying of paper products.
Para la produccion de papel con alta resistencia en seco es conocido aplicar sobre la superficie de papel ya secado, soluciones acuosas diluidas de almidon cocido o de polfmeros sinteticos, las cuales actuan respectivamente como agentes solidificantes de secado. Las cantidades de medio solidificante de secado son por norma de 0,1 a 6 % en peso, referido a papel seco. Dado que los agentes solidificantes de secado se aplican incluyendo el almidon en una solucion diluida acuosa - en general la concentracion de polfmero o de almidon de la solucion de preparacion acuosa es de entre 1 % y 10 % en peso - ha de evaporarse una cantidad importante de agua en el proceso de secado posterior. El paso de secado es por lo tanto muy costoso en terminos energeticos. La capacidad de las instalaciones de secado habituales en maquina para la fabricacion de papel, en muchos casos no obstante no es tan grande, como para que pudiese hacerse funcionar la maquina a la velocidad de produccion maxima posible. La velocidad de produccion de la maquina para la fabricacion de papel mas bien ha de reducirse, para que el papel se seque en la medida suficiente.For the production of paper with high dry strength it is known to apply on the surface of already dried paper, dilute aqueous solutions of cooked starch or synthetic polymers, which act respectively as solidifying agents for drying. The amounts of solidifying drying medium are usually 0.1 to 6% by weight, based on dry paper. Since the drying solidifying agents are applied including starch in a dilute aqueous solution - in general the concentration of polymer or starch in the aqueous preparation solution is between 1% and 10% by weight - a significant amount has to evaporate. of water in the subsequent drying process. The drying step is therefore very expensive in energetic terms. The capacity of the usual drying facilities in papermaking machine, in many cases, however, is not so large, that the machine could be operated at the maximum possible production speed. The speed of production of the papermaking machine must be reduced, so that the paper dries sufficiently.
Del documento de patente CA 1 110 019 se conoce un procedimiento para la produccion de papel con alta resistencia en seco, en el cual se anade al material de papel en primer lugar un polfmero cationico soluble en agua, por ejemplo, polietilenimina, y tras ello, se anade un polfmero anionico soluble en agua, por ejemplo, una poliacrilamida hidrolizada y se elimina el agua del material de papel en la maquina para la fabricacion de papel mediante la conformacion de hojas. Los polfmeros anionicos comprenden hasta 30 % en moles de acido acnlico introducido mediante polimerizacion.From the patent document CA 1 110 019 a process is known for the production of paper with high dry strength, in which a water-soluble cationic polymer is added to the paper material, for example, polyethyleneimine, and after that , a water-soluble anionic polymer is added, for example, a hydrolyzed polyacrylamide and water is removed from the paper material in the papermaking machine by forming sheets. Anionic polymers comprise up to 30 mol% of acrylic acid introduced by polymerization.
Del documento DE-A 35 06 832 se conoce un procedimiento para la produccion de papel con alta resistencia en seco, en el cual en primer lugar se anade al material de papel un polfmero cationico soluble en agua, y a continuacion, un polfmero anionico soluble en agua. Como polfmeros anionicos se tienen en consideracion por ejemplo, homo o copolfmeros de acidos carbonicos C3 - C5 etilenicamente insaturados. Los copolfmeros comprenden al menos un 35 % en peso de un acido carbonico C3 - C5 etilenicamente insaturado (por ejemplo, acido acnlico) introducido mediante polimerizacion. Como polfmeros cationicos se describen en los ejemplos, polietilenimina, polivinilamina, cloruro de polidialildimetilamonio y productos de condensacion reticulados con epiclorhidrina, de acido adfpico y dietilentriamina. Tambien se tiene en consideracion el uso de homo y copolfmeros parcialmente hidrolizados de la N-vinilformamida. El grado de hidrolisis de los polfmeros de N-vinilformamida es en este caso de al menos 30 % en moles y es de preferentemente 50 a 100 % en moles.From DE-A 35 06 832 a process is known for the production of paper with high dry strength, in which first a water-soluble cationic polymer is added to the paper material, and then an anionic polymer soluble in Water. As anionic polymers, for example, homo or copolymers of ethylenically unsaturated C3-C5 carbonic acids are considered. The copolymers comprise at least 35% by weight of an ethylenically unsaturated C3-C5 carbonic acid (for example, acrylic acid) introduced by polymerization. As cationic polymers, polyethyleneimine, polyvinylamine, polydiallyldimethylammonium chloride and condensation products cross-linked with epichlorohydrin, adipic acid and diethylenetriamine are described in the examples. The use of partially hydrolyzed homo and copolymers of N-vinylformamide is also considered. The degree of hydrolysis of the polymers of N-vinylformamide is in this case at least 30 mol% and is preferably 50 to 100 mol%.
El documento JP-A 1999-140787 se refiere a un procedimiento para la produccion de cartulina ondulada, anadiendose para la mejora de las propiedades de resistencia de un producto de papel, de 0,05 a 0,5 % en peso, referido al material de papel a secar, de una polivinilamina, al material de papel, la cual es accesible mediante hidrolisis de polivinilformamida con un grado de hidrolisis de 25 a 100 %, en combinacion con una poliacrilamida anionica, eliminandose entonces el agua del material de papel y secandose.JP-A 1999-140787 refers to a process for the production of corrugated cardboard, in addition to improving the strength properties of a paper product, from 0.05 to 0.5% by weight, based on the material of paper to be dried, of a polyvinylamine, to the paper material, which is accessible by hydrolysis of polyvinylformamide with a degree of hydrolysis of 25 to 100%, in combination with an anionic polyacrylamide, then removing water from the paper material and drying .
Del documento WO 03/052206 se conoce un producto de papel con propiedades de resistencia mejoradas, el cual puede obtenerse debido a que se aplica sobre la superficie de un producto de papel una polivinilamina y un compuesto anionico polimerico, el cual puede conformar con polivinilamina un complejo de polielectrolito, o un compuesto polimerico con funciones de aldehudo, como polisacaridos con contenido de grupos de aldehudo. No solo se alcanza una mejora de la resistencia en seco y en humedo del papel, sino que se observa tambien un efecto de encolado de los medios de tratamiento.From WO 03/052206 a paper product with improved strength properties is known, which can be obtained because a polyvinylamine and a polymeric anionic compound are applied on the surface of a paper product, which can form a polyvinyl amine polyelectrolyte complex, or a polymeric compound with aldehyde functions, such as polysaccharides containing aldehyde groups. Not only is an improvement in the dry and wet strength of the paper achieved, but also a sizing effect of the treatment means is observed.
El documento DE 195 370 88 divulga un procedimiento para la produccion de papel provisto de resistencia en seco y de resistencia en humedo mediante la adicion de combinaciones a partir de poliisocianatos modificados hidrofilamente y polfmeros que comprenden unidades de vinilamina.DE 195 370 88 discloses a process for the production of paper provided with dry strength and wet strength by adding combinations from hydrophilically modified polyisocyanates and polymers comprising vinylamine units.
El documento EP 672 212 divulga el uso unico de copolfmeros hidrolizados de amidas de acido N-vinilcarboxflico y acidos carboxflicos no saturados monoetilenicamente como aditivo para el material de papel.EP 672 212 discloses the unique use of hydrolyzed copolymers of N-vinylcarboxylic acid amides and monoethylenically unsaturated carboxylic acids as an additive for the paper material.
El documento EP 362 770 y el documento EP 723 047 divulgan respectivamente combinaciones de poliacrilamidas y sulfonato de lignina, las cuales anteriormente se producen como complejo de polielectrolito y como tal se anaden al material de papel. Ambos documentos divulgan ademas de ello, la adicion de alumbre, lo cual da como resultado el aumento del valor de pH. El experto conoce el uso de alumbre como agente de fijacion, para fijar el complejo de polielectrolito a partir de poliacrilamida y sulfonato de lignina sobre la fibra.EP 362 770 and EP 723 047 disclose respectively combinations of polyacrylamides and lignin sulphonate, which are previously produced as a polyelectrolyte complex and as such are added to the paper material. Both documents also disclose the addition of alum, which results in an increase in the pH value. The expert knows the use of alum as a fixing agent, to fix the polyelectrolyte complex from polyacrylamide and lignin sulphonate on the fiber.
Del documento WO 04/061235 se conoce un procedimiento para la produccion de papel, en particular panuelos, con resistencias en humedo y/o en seco particularmente altas, en el cual se anade al material de papel en primer lugar un polfmero cationico soluble en agua, el cual comprende al menos 1,5 meq/g de polfmero con funcionalidadesFrom WO 04/061235 a process is known for the production of paper, in particular panuelos, with particularly high wet and / or dry strengths, in which a water-soluble cationic polymer is added to the paper material first , which comprises at least 1.5 meq / g of polymer with functionalities
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ammicas primarias y presenta un peso molecular de al menos 10.000 Dalton. Se resaltan particularmente en este caso homopoKmeros parcial o completamente hidrolizados de la N-vinilformamida. A continuacion, se anade un polfmero anionico soluble en agua, el cual comprende grupos anionicos y/o aldehudicos. Como ventaja de este procedimiento resulta sobre todo la variabilidad de los sistemas de dos componentes descritos en lo que se refiere a diferentes propiedades de papel, entre ellas, resistencia en humedo y en seco.primary ammic and has a molecular weight of at least 10,000 Daltons. Particularly in this case, partially or completely hydrolysed homopoKers of N-vinylformamide are particularly prominent. Next, a water-soluble anionic polymer is added, which comprises anionic and / or aldehyde groups. As an advantage of this procedure, the variability of the two-component systems described in regard to different paper properties, including wet and dry strength, results above all.
Del documento EP-A 438 744 se conoce el uso de copolfmeros a partir de por ejemplo, N-vinilformamida y acido acnlico, acido metacnlico y/o acido maleico con un valor K de 8 a 50 (determinado segun H. Fikentscher en solucion acuosa de 1 % con pH 7 y 25 °C), asf como los polfmeros que pueden obtenerse a partir de ello mediante separacion parcial o completa de grupos formilo de la vinilformamida polimerizada mediante la conformacion de unidades de vinilamina, como impedidor de capa en sistemas de conduccion de agua, como calderas o tubos.From EP-A 438 744 the use of copolymers is known from, for example, N-vinylformamide and acrylic acid, methacrylic acid and / or maleic acid with a K value of 8 to 50 (determined according to H. Fikentscher in aqueous solution of 1% with pH 7 and 25 ° C), as well as the polymers that can be obtained therefrom by partial or complete separation of formyl groups from the polymerized vinylformamide by forming vinylamine units, as a layer inhibitor in systems of water conduction, such as boilers or pipes.
Es conocido ademas de ello, que pueden usarse copolfmeros, los cuales pueden obtenerse mediante copolimerizacion de amidas de acido N-vinilcarboxflico, acidos carboxflicos monoetilenicamente insaturados y eventualmente otros monomeros etilenicamente insaturados e hidrolisis posterior de las unidades de acido vinilcarboxflico comprendido en los copolfmeros dando lugar a las correspondientes unidades de aminas o amonio, durante la produccion de papel como aditivo al material de papel para el aumento de la velocidad de eliminacion de agua y la retencion asf como resistencia en seco y en humedo del papel, comparese el documento EP-B 672 212.It is also known that copolymers can be used, which can be obtained by copolymerization of N-vinylcarboxylic acid amides, monoethylenically unsaturated carboxylic acids and possibly other ethylenically unsaturated monomers and subsequent hydrolysis of the vinylcarboxylic acid units comprising the copolymers. to the corresponding units of amines or ammonium, during the production of paper as an additive to the paper material for increasing the rate of water removal and retention as well as dry and wet strength of the paper, compare document EP-B 672 212.
Del documento de solicitud anterior DE 10 2004 056 551.1 se conoce un procedimiento para la produccion de papel, cartulina y carton con alta resistencia en seco mediante adicion por separado de un polfmero que comprende unidades de vinilamina y de un compuesto anionico polimerico a un material de papel, eliminacion de agua del material de papel y secado de los productos de papel. En este caso se usa como compuesto anionico polimerico al menos un copolfmero, el cual puede obtenerse mediante la copolimerizacion deFrom the previous application document DE 10 2004 056 551.1 a process for the production of paper, cardboard and cardboard with high dry strength is known by separately adding a polymer comprising vinylamine units and a polymeric anionic compound to a material of paper, water removal from paper material and drying of paper products. In this case, at least one copolymer is used as the polymeric anionic compound, which can be obtained by the copolymerization of
(a) al menos una amida de acido N-vinilcarboxflico de la formula(a) at least one N-vinylcarboxylic acid amide of the formula
significando en la misma R1, R2 = H o alquilo de C1 a C6,meaning therein R1, R2 = H or C1 to C6 alkyl,
(b) al menos un monomero monoetilenicamente insaturado que comprende grupos acidos y/o sus sales de metal alcalino, de metal alcalinoterreo o de amonio y eventualmente(b) at least one monoethylenically unsaturated monomer comprising acid groups and / or their alkali metal, alkaline earth metal or ammonium salts and possibly
(c) otros monomeros monoetilenicamente insaturados, y eventualmente(c) other monoethylenically unsaturated monomers, and eventually
(d) compuestos, los cuales presentan al menos dos enlaces dobles etilenicamente insaturados en la molecula.(d) compounds, which have at least two ethylenically unsaturated double bonds in the molecule.
Es conocido ademas de ello, usar acido sulfonico de lignina y sulfonatos de lignina como agente de dispersion en morteros de cemento y de yeso, como agentes de flotacion, como aditivo en el peleteado de alimento animal, como aglutinante de arenas de fundicion y como medio de aglomeracion en la fundicion de mineral, comparese Rompp, 9. Edicion, editorial Georg Thieme Verlag Stuttgart, 1990, pagina 2511.In addition, it is known to use lignin sulfonic acid and lignin sulphonates as a dispersing agent in cement and plaster mortars, as buoyancy agents, as an additive in animal feed pelleting, as a binder of foundry sands and as a medium. of agglomeration in the mineral smelter, compare Rompp, 9. Edition, editorial Georg Thieme Verlag Stuttgart, 1990, page 2511.
La presente invencion se basa en la tarea de poner a disposicion otro procedimiento para la produccion de papel con alta resistencia en seco y una resistencia en humedo lo mas baja posible. En este caso ha de continuar mejorandose frente a los procedimientos conocidos hasta ahora, la resistencia en seco, en particular en papeles de embalaje (por ejemplo, ondulacion de papel reciclado, acanalado).The present invention is based on the task of making available another process for the production of paper with high dry strength and a wet strength as low as possible. In this case, the dry strength, in particular in wrapping paper (for example, corrugated recycled paper, corrugated paper), has to continue to be improved in the face of the procedures known so far.
La tarea se soluciona segun la invencion con un procedimiento para la produccion de papel, cartulina y carton con alta resistencia en seco mediante la adicion por separado de un polfmero cationico con contenido de unidades de vinilamina y de un compuesto anionico polimerico a un material de papel, eliminacion del agua del material de papel y secado de los productos de papel, cuando se usa como compuesto anionico polimericoThe task is solved according to the invention with a process for the production of paper, cardboard and cardboard with high dry strength by separately adding a cationic polymer containing vinylamine units and a polymeric anionic compound to a paper material. , removal of water from paper material and drying of paper products, when used as a polymeric anionic compound
(i) acido lignosulfonico y/o un sulfonato de lignina y(i) lignosulfonic acid and / or a lignin sulphonate and
(ii) al menos un copolfmero, el cual se obtiene mediante la copolimerizacion de(ii) at least one copolymer, which is obtained by the copolymerization of
(a) al menos una amida de acido N-vinilcarboxflico de la formula(a) at least one N-vinylcarboxylic acid amide of the formula
significando en la misma R1, R2 = H o alquilo de C1 a C6,meaning therein R1, R2 = H or C1 to C6 alkyl,
(b) al menos un monomero monoetilenicamente insaturado que comprende grupos acidos y/o sus sales de metal alcalino, de metal alcalinoterreo o de amonio y eventualmente(b) at least one monoethylenically unsaturated monomer comprising acid groups and / or their alkali metal, alkaline earth metal or ammonium salts and possibly
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(c) otros monomeros monoetilenicamente insaturados, y eventualmente(c) other monoethylenically unsaturated monomers, and eventually
(d) compuestos, los cuales presentan al menos dos enlaces dobles etilenicamente insaturados en la molecula.(d) compounds, which have at least two ethylenically unsaturated double bonds in the molecule.
En el procedimiento segun la invencion se anade al material de papel como componente cationico polimerico un polfmero que comprende unidades de vinilamina. Estos compuestos se usan preferentemente como componente cationico unico. Pueden substituirse sin embargo eventualmente hasta una proporcion de 50 % en peso por otros polfmeros cationicos como poli(met)acrilamidas cationicas, cloruros de polidialildimetilamonio, condensados de dimetilamina y epiclorhidrina o polidialquil(met)acrilamidas.In the process according to the invention, a polymer comprising vinylamine units is added to the paper material as a polymeric cationic component. These compounds are preferably used as a single cationic component. However, up to a proportion of 50% by weight may be substituted by other cationic polymers such as cationic poly (meth) acrylamides, polydiallyldimethylammonium chlorides, dimethylamine and epichlorohydrin condensates or polydialkyl (meth) acrylamides.
Como polfmeros cationicos que comprenden unidades de vinilamina se adecuan todos los polfmeros, los cuales se indican por ejemplo citados en relacion con el estado de tecnica en el documento WO 04/061235, pagina 12, lmea 28 hasta la pagina 13, lmea 21, asf como en la figura 1. La masa molar Mw de los polfmeros que comprenden unidades de vinilamina es por ejemplo, de 1000 a 5 millones y se encuentra al menos en el rango de 5 000 a 500 000, preferentemente 40 000 D a 400 000 D.As cationic polymers comprising vinylamine units, all polymers are suitable, which are indicated, for example, in relation to the state of the art in WO 04/061235, page 12, line 28 to page 13, line 21, asf as in Figure 1. The Mw molar mass of polymers comprising vinylamine units is for example from 1000 to 5 million and is at least in the range of 5,000 to 500,000, preferably 40,000 D to 400,000 D .
Los polfmeros cationicos que comprenden unidades de vinilamina pueden obtenerse por ejemplo, mediante la polimerizacion de al menos un monomero de la formulaCationic polymers comprising vinylamine units can be obtained for example, by polymerizing at least one monomer of the formula
significando en la misma R1, R2 = H o alquilo de C1 a C6,meaning therein R1, R2 = H or C1 to C6 alkyl,
y separacion posterior parcial o completa de los grupos -CO-R1 de las unidades introducidas por polimerizacion en el polfmero, de los monomeros I con formacion de grupos amino. En la produccion de estos polfmeros pueden conformarse de forma conocida en una reaccion secundaria, de unidades de vinilamina y unidades de vinilformamida adyacentes, unidades de amida. Para los polfmeros cationicos aqu descritos, la indicacion de unidades de vinilamina comprende la suma de unidades de vinilamina y amida en polfmeros. Como polfmero que comprende unidades de vinilamina se usa por ejemplo, un homopolfmero hidrolizado de al menos 1 % en moles de N-vinilformamida. La polivinilamina y/o los homopolfmeros con un grado de hidrolisis de al menos 50 % en moles de la N-vinilformamida se usan en el procedimiento segun la invencion preferentemente como componente cationico.and subsequent partial or complete separation of the -CO-R1 groups from the units introduced by polymerization in the polymer, of the monomers I with amino group formation. In the production of these polymers, they can be formed in a known manner in a secondary reaction, from adjacent vinylamine units and vinylformamide units, amide units. For the cationic polymers described herein, the indication of vinylamine units comprises the sum of vinylamine and amide units in polymers. As the polymer comprising vinylamine units, for example, a hydrolyzed homopolymer of at least 1 mol% of N-vinylformamide is used. Polyvinylamine and / or homopolymers with a hydrolysis degree of at least 50 mol% of the N-vinylformamide are used in the process according to the invention preferably as a cationic component.
En el procedimiento segun la invencion pueden usarse como componente cationico tambien copolfmeros anfoteros, los cuales comprenden unidades de vinilamina y que presentan al menos 10 % en moles mas de grupos cationicos que anionicos. Este tipo de polfmeros anfoteros pueden obtenerse por ejemplo, por copolimerizacionIn the process according to the invention, amphoteric copolymers can also be used as a cationic component, which comprise vinylamine units and have at least 10 mol% more of cationic than anionic groups. This type of amphoteric polymers can be obtained, for example, by copolymerization.
(a) de al menos una amida de acido N-vinilcarboxflico de la formula(a) of at least one N-vinylcarboxylic acid amide of the formula
significando en la misma R1, R2 = H o alquilo de C1 a C6,meaning therein R1, R2 = H or C1 to C6 alkyl,
(b) al menos un monomero monoetilenicamente insaturado que comprende grupos acidos y/o sus sales de metal alcalino, de metal alcalinoterreo o de amonio y eventualmente(b) at least one monoethylenically unsaturated monomer comprising acid groups and / or their alkali metal, alkaline earth metal or ammonium salts and possibly
(c) otros monomeros monoetilenicamente insaturados, y eventualmente(c) other monoethylenically unsaturated monomers, and eventually
(d) compuestos, los cuales presentan al menos dos enlaces dobles etilenicamente insaturados en la molecula.(d) compounds, which have at least two ethylenically unsaturated double bonds in the molecule.
y separacion posterior parcial o completa de los grupos -CO-R1 de las unidades introducidas por polimerizacion en el polfmero, de los monomeros I con formacion de grupos amino, siendo la proporcion de los grupos amino en el copolfmero mayor a razon de al menos 10 % en moles, que la proporcion de las unidades de monomeros monoetilenicamente insaturados con contenido de grupos acidos.and partial or complete subsequent separation of the -CO-R1 groups from the units introduced by polymerization in the polymer, of the monomers I with amino group formation, the proportion of the amino groups in the copolymer being greater at the rate of at least 10 Mole%, than the proportion of monoethylenically unsaturated monomer units containing acidic groups.
Este grupo de polfmeros, los cuales son anfoteros y los cuales presentan en general mas grupos cationicos que anionicos, comprende por ejemplo, hasta como maximo 35 % en moles, preferentemente hasta como maximo 10 % en moles de al menos un monomero con contenido de grupos acidos del grupo (b) introducido mediante polimerizacion.This group of polymers, which are amphoteric and which generally have more cationic than anionic groups, comprises, for example, up to a maximum of 35 mol%, preferably up to a maximum of 10 mol% of at least one monomer containing groups. acids from group (b) introduced by polymerization.
Como compuesto anionico polimerico se tiene en consideracion segun la invencion acido lignosulfonico y/o un sulfonato de lignina. Se dan indicaciones mas detalladas con respecto a estos productos, por ejemplo, en el puntoAs the polymeric anionic compound, lignosulfonic acid and / or a lignin sulphonate are considered according to the invention. More detailed indications are given regarding these products, for example, in the point
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literario indicado mas arriba Rompp, 9. Edicion, editorial G. Thieme Verlag Stuttgart, 1990, pagina 2511 y en Ullmann’s Encyclopedia of Industrial Chemistry, 5. Completely Revised Edition, volumen A15, paginas 311 a 314. El acido lignosulfonico resulta durante la produccion de celulosa mediante disgregacion de sulfito de madera, reaccionando la lignina con acido sulfurico. Se sulfona en este caso en las cadenas laterales C3 de las unidades de fenilpropano. En dependencia de las sustancias qmmicas usadas en la disgregacion de la madera, resultan en este caso acido lignosulfonico o sulfonatos de lignina, por ejemplo, las sales de sodio, potasio, amonio, magnesio o calcio del acido lignosulfonico. El acido lignosulfonico, asf como las sales mencionadas del acido lignosulfonico son solubles en agua. La masa molar del acido lignosulfonico es de por ejemplo, 10 000 a 200 000 g/mol. Los sulfonatos de lignina se obtienen por ejemplo, de las lejfas al sulfito (lejia negra) de la produccion de celulosa.literary indicated above Rompp, 9. Edition, editorial G. Thieme Verlag Stuttgart, 1990, page 2511 and in Ullmann's Encyclopedia of Industrial Chemistry, 5. Completely Revised Edition, volume A15, pages 311 to 314. Lignosulfonic acid results during production of cellulose by disintegration of wood sulphite, reacting lignin with sulfuric acid. It is sulfonated in this case in the C3 side chains of the phenylpropane units. Depending on the chemical substances used in the disintegration of wood, lignosulfonic acid or lignin sulphonates result in this case, for example, the sodium, potassium, ammonium, magnesium or calcium salts of lignosulfonic acid. Lignosulfonic acid, as well as the mentioned salts of lignosulfonic acid are soluble in water. The molar mass of lignosulfonic acid is, for example, 10,000 to 200,000 g / mol. Lignin sulphonates are obtained, for example, from sulphite (black liquor) lejfas from cellulose production.
En el procedimiento segun la invencion se dosifica por ejemplo a un material de papel, sucesivamente acido lignosulfonico y/o al menos un sulfonato de lignina y tras ello al menos un polfmero con contenido de unidades de vinilamina. Puede anadirse no obstante tambien en primer lugar un polfmero con contenido de unidades de vinilamina y a continuacion acido lignosulfonico y/o un sulfonato de lignina a un material de papel y entonces eliminarse el agua mediante la conformacion de hojas. Esencial es solo que se dosifiquen por separado entre sf polfmero cationico y el componente anionico. El acido lignosulfonico, y/o el sulfonato de lignina se usan por ejemplo, en una cantidad de 0,1 a 10 % en peso, preferentemente de 0,2 a 5 % en peso y en particular de 0,5 a 2 % en peso, referido al material de papel seco.In the process according to the invention, for example, a paper material, successively lignosulfonic acid and / or at least one lignin sulphonate is dosed and then at least one polymer containing vinylamine units. However, a polymer containing vinylamine units and then lignosulfonic acid and / or a lignin sulphonate can also be added first to a paper material and then the water removed by sheet forming. Essential is that they are dosed separately between the cationic polymer and the anionic component. Lignosulfonic acid, and / or lignin sulphonate are used, for example, in an amount of 0.1 to 10% by weight, preferably 0.2 to 5% by weight and in particular 0.5 to 2% in weight, referred to the dry paper material.
Como sulfonato de lignina se usan por ejemplo las sales de sodio, de potasio, de amonio, de calcio, de magnesio solubles en agua o sus mezclas. Preferentemente se usan las sales de sodio, de amonio y de calcio.As lignin sulphonate, for example, sodium, potassium, ammonium, calcium, magnesium salts soluble in water or mixtures thereof are used. Preferably the sodium, ammonium and calcium salts are used.
El polfmero con contenido de unidades de vinilamina y el acido lignosulfonico y/o el sulfonato de lignina se usan en el procedimiento segun la invencion por ejemplo en la proporcion de peso 5 : 1 a 1 : 5, preferentemente en la proporcion de peso 2 : 1 a 1 : 2.The polymer containing vinylamine units and lignosulfonic acid and / or lignin sulphonate are used in the process according to the invention for example in the weight ratio 5: 1 to 1: 5, preferably in the weight ratio 2: 1 to 1: 2.
Segun la invencion se usa acido lignosulfonico y/o sulfonato de lignina junto con un polfmero anionico de una amida de acido N-vinilcarboxflico. La dosificacion de estos dos componentes puede producirse en este caso por separado o tambien como mezcla. Preferentemente se dosifica no obstante en primer lugar, sulfonato de lignina y a continuacion, el polfmero anionico, el orden de dosificacion de estos compuestos puede no obstante tambien invertirse. De esta manera se usa segun la invencion por ejemplo como compuesto anionico polimericoAccording to the invention, lignosulfonic acid and / or lignin sulphonate are used together with an anionic polymer of an N-vinylcarboxylic acid amide. The dosing of these two components can occur in this case separately or also as a mixture. Preferably, however, first, lignin sulphonate is dosed and then the anionic polymer, the dosage order of these compounds can, however, also be reversed. In this way it is used according to the invention for example as a polymeric anionic compound
(i) acido lignosulfonico y/o un sulfonato de lignina y(i) lignosulfonic acid and / or a lignin sulphonate and
(ii) al menos un copolfmero, el cual se obtiene mediante la copolimerizacion de(ii) at least one copolymer, which is obtained by the copolymerization of
(a) al menos una amida de acido N-vinilcarboxflico de la formula(a) at least one N-vinylcarboxylic acid amide of the formula
CH =CH— , (I).CH = CH—, (I).
''CO—R'' CO — R
significando en la misma R1, R2 = H o alquilo de C1 a C6,meaning therein R1, R2 = H or C1 to C6 alkyl,
(b) al menos un monomero monoetilenicamente insaturado que comprende grupos acidos y/o sus sales de metal alcalino, de metal alcalinoterreo o de amonio y eventualmente(b) at least one monoethylenically unsaturated monomer comprising acid groups and / or their alkali metal, alkaline earth metal or ammonium salts and possibly
(c) otros monomeros monoetilenicamente insaturados, y eventualmente(c) other monoethylenically unsaturated monomers, and eventually
(d) compuestos, los cuales presentan al menos dos enlaces dobles etilenicamente insaturados en la molecula.(d) compounds, which have at least two ethylenically unsaturated double bonds in the molecule.
Preferentemente se usa como compuesto anionico (ii) un copolfmero, el cual se obtiene mediante la copolimerizacion dePreferably, a copolymer is used as an anionic compound (ii), which is obtained by the copolymerization of
(a) N-vinilformamida(a) N-vinylformamide
(b) acido acnlico, acido metacnlico, y/o sus sales alcalinas o de amonio y eventualmente(b) Acrylic acid, methacrylic acid, and / or its alkaline or ammonium salts and possibly
(c) otros monomeros monoetilenicamente insaturados.(c) other monoethylenically unsaturated monomers.
El compuesto anionico polimerico (ii) comprende por ejemplo,The polymeric anionic compound (ii) comprises, for example,
(a) de 10 a 95 % en moles de unidades de la formula I(a) 10 to 95 mol% of units of formula I
(b) de 5 a 90 % en moles de unidades de un acido carbonico monoetilenicamente insaturado con de 3 a 8 atomos de C en la molecula y/o sus sales de metal alcalino, de metal alcalinoterreo o de amonio y(b) 5 to 90 mol% of units of a monoethylenically unsaturated carbonic acid with 3 to 8 atoms of C in the molecule and / or its alkali metal, alkaline earth metal or ammonium salts and
(c) de 0 a 30 % en moles de unidades de al menos otro monomero monoetilenicamente insaturado.(c) from 0 to 30 mol% of units of at least one other monoethylenically unsaturated monomer.
Estos compuestos pueden estar modificados en cuanto que comprenden adicionalmente tambien al menos un compuesto con al menos dos enlaces dobles etilenicamente insaturados introducido mediante polimerizacion en la molecula. Si se copolimerizan los monomeros (a) y (b) o (a), (b) y (c) en presencia de un compuesto de este tipo, se obtienen copolfmeros ramificados. En este caso han de elegirse las proporciones de cantidad y las condiciones deThese compounds may be modified in that they additionally also comprise at least one compound with at least two ethylenically unsaturated double bonds introduced by polymerization in the molecule. If the monomers (a) and (b) or (a), (b) and (c) are copolymerized in the presence of such a compound, branched copolymers are obtained. In this case, the quantity proportions and the conditions of
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reaccion de tal manera, que se continuen manteniendo poKmeros solubles en agua. En determinadas condiciones puede ser necesario para ello el uso de reguladores de polimerizacion. Pueden usarse todos los reguladores conocidos, como por ejemplo, tioles, alcoholes sec., sulfitos, fosfitos, hipofosfitos, tioacidos, aldehndos, etc. (mas indicaciones por ejemplo, en el documento EP-A 438 744, pagina 5, lmeas 7-12). Los copoKmeros ramificados comprenden poKmeros por ejemploreaction in such a way that they continue to maintain water soluble poKmeros. Under certain conditions, the use of polymerization regulators may be necessary. All known regulators can be used, such as thiols, sec. Alcohols, sulphites, phosphites, hypophosphites, thioacids, aldehydes, etc. (more indications for example, in document EP-A 438 744, page 5, lines 7-12). Branched copoKers comprise poKmeros for example
(a) de 10 a 95 % en moles de unidades de la formula I(a) 10 to 95 mol% of units of formula I
(b) de 5 a 90 % en moles de unidades de un monomero monoetilenicamente insaturado que comprende grupos acidos y/o sus sales de metal alcalino, de metal alcalinoterreo o de amonio(b) 5 to 90 mol% of units of a monoethylenically unsaturated monomer comprising acid groups and / or their alkali metal, alkaline earth metal or ammonium salts
(c) de 0 a 30 % en moles de unidades de al menos otro monomero monoetilenicamente insaturado y(c) from 0 to 30 mol% of units of at least one other monoethylenically unsaturated monomer and
(d) de 0 a 2 % en moles, preferentemente de 0,001 a 1 % en moles de al menos un compuesto con al menos dos enlaces dobles etilenicamente insaturados.(d) 0 to 2 mol%, preferably 0.001 to 1 mol% of at least one compound with at least two ethylenically unsaturated double bonds.
Son ejemplos de monomeros del grupo (a) N-vinilformamida, N-vinil-N-metilformamida, N-vinilacetamida, N-vinil-N- metilacetamida, N-vinil-N-metilpropionamida y N-vinilpropionamida. Los monomeros del grupo (a) pueden usarse solos o mezclados en la copolimerizacion con los monomeros de los otros grupos.Examples of monomers of the group (a) are N-vinylformamide, N-vinyl-N-methylformamide, N-vinyl acetamide, N-vinyl-N-methylacetamide, N-vinyl-N-methylpropionamide and N-vinylpropionamide. The monomers of group (a) can be used alone or mixed in the copolymerization with the monomers of the other groups.
Como monomeros del grupo (b) se tienen en consideracion en particular acidos carboxflicos monoetilenicamente insaturados con de 3 a 8 atomos de C, asf como las sales solubles en agua de estos acidos carboxflicos. A este grupo de monomeros pertenecen por ejemplo, acido acnlico, acido metacnlico, acido dimetacnlico, acido etacnlico, acido maleico, acido fumarico, acido itaconico, acido mesaconico, acido citraconico, acido metilmalonico, acido alilacetico, acido vinilacetico y acido crotonico. Como monomeros del grupo (b) se adecuan ademas de ello monomeros con contenido de grupos sulfonicos, como acido vinilsulfonico, acido sulfonico de acrilamido-2- metilpropano y acido sulfonico de estireno, asf como acido vinilfosfonico. Los monomeros de este grupo pueden usarse solos o mezclados entre sf, en forma neutralizada parcial o totalmente, en la copolimerizacion. Para la neutralizacion se usan por ejemplo, bases de metal alcalino o de metal alcalinoterreo, amoniaco, aminas y/o alcanolaminas. Ejemplos de ello son solucion acuosa de hidroxido sodico, solucion acuosa de hidroxido de potasio, natron, potasa, hidrogenocarbonato de sodio, oxido de magnesio, hidroxido de calcio, oxido de calcio, trietanolamina, etanolamina, morfolina, dietilentriamina o tetraetilpentamina. Los monomeros del grupo (b) se usan durante la copolimerizacion preferentemente en forma parcialmente neutralizada.As monomers of group (b), monoethylenically unsaturated carboxylic acids with 3 to 8 C atoms are taken into consideration, as well as the water soluble salts of these carboxylic acids. To this group of monomers belong, for example, acrylic acid, methacrylic acid, dimethacrylic acid, ethacrylic acid, maleic acid, smoking acid, itaconic acid, mesaconic acid, citraconic acid, methylmalonic acid, allylacetic acid, vinyl acetic acid and crotonic acid. In addition, as monomers of group (b), monomers containing sulfonic groups are suitable, such as vinyl sulfonic acid, acrylamido-2-methylpropane sulfonic acid and styrene sulfonic acid, as well as vinyl phosphonic acid. The monomers of this group can be used alone or mixed with each other, partially or totally neutralized, in the copolymerization. For neutralization, for example, alkali metal or alkaline earth metal bases, ammonia, amines and / or alkanolamines are used. Examples are aqueous solution of sodium hydroxide, aqueous solution of potassium hydroxide, natron, potash, sodium hydrogen carbonate, magnesium oxide, calcium hydroxide, calcium oxide, triethanolamine, ethanolamine, morpholine, diethylenetriamine or tetraethylpentamine. The monomers of group (b) are used during copolymerization preferably in partially neutralized form.
Los copolfmeros pueden comprender para la modificacion eventualmente monomeros del grupo (c) de forma polimerizada, por ejemplo, ester de acidos carboxflicos C3 a C5 etilenicamente insaturados, como acrilato de metilo, acrilato de etilo, acrilato de n-butilo, acrilato de isobutilo, metacrilato de isobutilo, metacrilato de metilo, metacrilato de etilo, asf como ester de vinilo, como acetato de vinilo o propionato de vinilo, u otros monomeros como N- vinilpirrolidona, acrilamida y/o metacrilamida.The copolymers may comprise, for the modification, optionally monomers of the group (c) in a polymerized form, for example, ester of ethylenically unsaturated C3 to C5 carboxylic acids, such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, isobutyl methacrylate, methyl methacrylate, ethyl methacrylate, as well as vinyl ester, such as vinyl acetate or vinyl propionate, or other monomers such as N-vinyl pyrrolidone, acrylamide and / or methacrylamide.
Otra modificacion de los copolfmeros es posible debido a que se usan durante la copolimerizacion monomeros (d), los cuales comprenden al menos dos enlaces dobles en la molecula, por ejemplo, metilenbisacrilamida, diacrilato de glicol, dimetacrilato de glicol, triacrilato de glicerina, trietilamina, alileter de pentaeritritol, polialquilenglicoles esterificados al menos dos veces con acido acnlico y/o acido metacnlico o polioles como pentaeritritol, sorbitol o glucosa. En caso de que se use al menos un monomero del grupo (d) en la copolimerizacion, las cantidades usadas son de hasta 2 % en moles, por ejemplo, 0,001 a 1 % en moles.Another modification of the copolymers is possible because monomers (d) are used during copolymerization, which comprise at least two double bonds in the molecule, for example, methylene bisacrylamide, glycol diacrylate, glycol dimethacrylate, glycerine triacrylate, triethylamine , pentaerythritol, polyalkylene glycols esterified at least twice with acrylic acid and / or methacrylic acid or polyols such as pentaerythritol, sorbitol or glucose. In case at least one monomer of group (d) is used in the copolymerization, the amounts used are up to 2 mol%, for example, 0.001 to 1 mol%.
La copolimerizacion de los monomeros se produce de forma conocida en presencia de iniciadores de polimerizacion radicales y eventualmente en presencia de reguladores de polimerizacion, comparese EP-B 672 212, pagina 4, lmeas 13-37 o EP-A 438 744, pagina 2, lmea 26 a pagina 8, lmea 18.Copolymerization of the monomers occurs in a known manner in the presence of radical polymerization initiators and possibly in the presence of polymerization regulators, compare EP-B 672 212, page 4, lines 13-37 or EP-A 438 744, page 2, line 26 to page 8, line 18.
Como compuesto anionico polimerico (ii) se usa preferentemente un copolfmero, el cual comprendeAs a polymeric anionic compound (ii) a copolymer is preferably used, which comprises
(a) de 50 a 90 % en moles de N-vinilformamida,(a) 50 to 90 mol% of N-vinylformamide,
(b) de 10 a 50 % en moles de acido acnlico, acido metacnlico y o sus sales alcalinas o de amonio, y eventualmente(b) 10 to 50 mol% of acrylic acid, methacrylic acid and or its alkaline or ammonium salts, and possibly
(c) de 0 a 30 % en moles de al menos otro monomero monoetilenicamente insaturado introducido mediante polimerizacion.(c) 0 to 30 mol% of at least one other monoethylenically unsaturated monomer introduced by polymerization.
Las masas molares Mw medias de los polfmeros anionicos (ii) son de por ejemplo, 30 000 D a 10 millones D, preferentemente de 100 000 D a 1 millon D. Estos polfmeros tienen por ejemplo valores K (determinado segun H. Fikentscher en solucion salina acuosa del 5 % con pH 7, una concentracion polimerica de 0,05 % en peso y una temperatura de 25 °C) en el rango de 20 a 250, preferentemente de 50 a 150.The average Mw molar masses of the anionic polymers (ii) are, for example, 30,000 D to 10 million D, preferably 100,000 D to 1 million D. These polymers have for example K values (determined according to H. Fikentscher in solution 5% aqueous saline with pH 7, a polymer concentration of 0.05% by weight and a temperature of 25 ° C) in the range of 20 to 250, preferably 50 to 150.
Es tambien objeto de la invencion el uso de un compuesto anionico polimerico segun la invencion como aditivo del material de papel en la produccion de papel, cartulina y carton en presencia de al menos un polfmero cationico que comprende unidades de vinilamina, para el aumento de la resistencia en seco.The use of a polymeric anionic compound according to the invention as an additive of the paper material in the production of paper, cardboard and cardboard in the presence of at least one cationic polymer comprising vinylamine units is also object of the invention. dry strength
En una forma de realizacion preferida de la invencion se dosifica en primer lugar acido lignosulfonico y/o sulfonato de lignina al material de papel, se anade entonces el polfmero que contiene unidades de vinilamina y a continuacion se elimina el agua del material de papel. Es particularmente preferida una forma de realizacion del procedimientoIn a preferred embodiment of the invention, lignosulfonic acid and / or lignin sulphonate are first dosed to the paper material, then the polymer containing vinylamine units is added and then the water is removed from the paper material. Particularly preferred is an embodiment of the process.
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segun la invencion, en la cual se anade tras haberse anadido acido lignosulfonico y/o sulfonato de lignina y al menos un poKmero con contenido de unidades de vinilamina al material de papel, tambien un copolfmero anionico con contenido de unidades de amida de acido vinilcarboxflico, el cual puede obtenerse mediante la copolimerizacion deaccording to the invention, in which it is added after lignosulfonic acid and / or lignin sulfonate have been added and at least one polymer containing vinylamine units to the paper material, also an anionic copolymer containing vinylcarboxylic acid amide units, which can be obtained by copolymerization of
(a) al menos una amida de acido N-vinilcarboxflico de la formula(a) at least one N-vinylcarboxylic acid amide of the formula
significando en la misma R1, R2 = H o alquilo de C1 a Ca,meaning therein R1, R2 = H or C1 to Ca alkyl,
(b) al menos un monomero monoetilenicamente insaturado que comprende grupos acidos y/o sus sales de metal(b) at least one monoethylenically unsaturated monomer comprising acidic groups and / or their metal salts
alcalino, de metal alcalinoterreo o de amonio y eventualmentealkaline, alkaline earth metal or ammonium and eventually
(c) otros monomeros monoetilenicamente insaturados, y eventualmente(c) other monoethylenically unsaturated monomers, and eventually
(d) compuestos, los cuales presentan al menos dos enlaces dobles etilenicamente insaturados en la molecula. Tras ello se elimina el agua del material de papel.(d) compounds, which have at least two ethylenically unsaturated double bonds in the molecule. After that the water is removed from the paper material.
Como materiales de fibra para la produccion de las pulpas, se tienen en consideracion todas las calidades que se pueden usar para ello, por ejemplo, material de madera, celulosa blanqueada y no blanqueada, asf como materiales de papel a partir de plantas anuales. Forman parte del material de madera por ejemplo, pulpa de madera, material termomecanico (TMP), material quimiotermomecanico (CTMP), pulpa impresa, papel semiqmmico, celulosa de alto rendimiento, y pulpa refinada mecanicamente (RMP). Como celulosa se tiene en consideracion por ejemplo, pasta al sulfato, al sulfito y al natron. Preferentemente se usa la celulosa no blanqueada, la cual se denomina tambien como celulosa Kraft o un material de papel a partir de residuos de papel. Las plantas anuales adecuadas para la produccion de materiales de papel son por ejemplo, arroz, trigo, cana de azucar y kenaf. Para la produccion de pulpas se usan habitualmente residuos de papel, los cuales se usan o bien solos, o mezclados con otros materiales de fibra o se parte de mezclas de fibras a partir de un material primario y producto defectuoso pintado retroalimentado, por ejemplo, sulfato de pino blanqueado mezclado con producto defectuoso pintado retroalimentado. La eliminacion del agua del material de papel se produce habitualmente sobre el filtro de una maquina para la fabricacion de papel. El procedimiento segun la invencion tiene importancia en particular para la produccion de papel y cartulina a partir de residuos de papel, dado que aumenta notablemente las propiedades de resistencia de las fibras retroalimentadas.As fiber materials for pulp production, all qualities that can be used for this are taken into account, for example, wood material, bleached and unbleached cellulose, as well as paper materials from annual plants. They are part of the wood material, for example, wood pulp, thermomechanical material (TMP), chemothermal material (CTMP), printed pulp, semi-chemical paper, high performance cellulose, and mechanically refined pulp (RMP). As cellulose, for example, sulfate, sulphite and natron pulp are considered. Preferably, non-bleached cellulose is used, which is also referred to as Kraft cellulose or a paper material from paper waste. Annual plants suitable for the production of paper materials are, for example, rice, wheat, sugar cane and kenaf. For the production of pulps, paper waste is usually used, which is used either alone, or mixed with other fiber materials or based on mixtures of fibers from a primary material and defective product painted back-fed, for example, sulfate of bleached pine mixed with defective product painted back. The elimination of water from the paper material usually occurs on the filter of a machine for the manufacture of paper. The method according to the invention is of particular importance for the production of paper and paperboard from paper waste, since the resistance properties of the fed fibers are markedly increased.
El valor de pH de la suspension de material se encuentra por ejemplo, en el rango de 4,5 a 8, habitualmente en de a a 7,5. Para el ajuste del valor de pH puede usarse por ejemplo, un acido como acido sulfurico o sulfato de aluminio.The pH value of the material suspension is, for example, in the range of 4.5 to 8, usually in a to 7.5. For the adjustment of the pH value, for example, an acid such as sulfuric acid or aluminum sulfate can be used.
El polfmero que comprende unidades de vinilamina, es decir, el componente cationico de los polfmeros a dosificar al material de papel, se anade en el procedimiento segun la invencion por ejemplo, a la materia consistente o preferentemente a una materia diluida. El punto de adicion se encuentra preferentemente antes del siete, pero puede encontrarse no obstante tambien entre un nivel de cizallamiento y una pantalla o despues. El componente anionico se dosifica preferentemente a la materia diluida.The polymer comprising vinylamine units, that is, the cationic component of the polymers to be dosed to the paper material, is added in the process according to the invention, for example, to the matter consistent or preferably to a diluted matter. The point of addition is preferably before seven, but it can nevertheless also be found between a shear level and a screen or after. The anionic component is preferably dosed to the diluted matter.
En una forma de realizacion particularmente preferida del procedimiento segun la invencion, se dosifica en primer lugar acido lignosulfonico o sulfonato de lignina, despues de ello, como componente cationico unico un polfmero con contenido de grupos de vinilamina y a continuacion, un polfmero anionico de vinilformamida. Puede anadirse no obstante tambien en primer lugar primero el componente cationico (polfmero con contenido de unidades de vinilamina como componente cationico unico) al material de papel y el componente anionico dosificarse al mismo tiempo, no obstante por separado del componente cationico, al material de papel. El polfmero con contenido de unidades de vinilamina se usa por ejemplo, en una cantidad de 0,05 a 2,0 % en peso, preferentemente de 0,1 a 1 % en peso referido a material de papel en seco. La proporcion de componente cationico (polfmero con contenido de unidades de vinilamina) con respecto a componente anionico polimerico (acido lignosulfonico y/o sulfonato de lignina o combinacion de acido lignosulfonico y/o sulfonato de lignina con al menos un polfmero anionico de vinilformamida) es de por ejemplo, 5 : 1 a 1 : 5 y se encuentra preferentemente en el rango de 2 : 1a 1 : 2.In a particularly preferred embodiment of the process according to the invention, lignosulfonic acid or lignin sulfonate is dosed first, thereafter, as a single cationic component, a polymer containing vinylamine groups and then, an anionic vinylformamide polymer. However, the cationic component (polymer containing vinylamine units as a single cationic component) can also be added first to the paper material and the anionic component dosed at the same time, however separately from the cationic component, to the paper material . The polymer containing vinylamine units is used, for example, in an amount of 0.05 to 2.0% by weight, preferably 0.1 to 1% by weight, based on dry paper material. The proportion of cationic component (polymer containing vinylamine units) with respect to polymeric anionic component (lignosulfonic acid and / or lignin sulphonate or combination of lignosulfonic acid and / or lignin sulphonate with at least one anionic vinylformamide polymer) is for example, 5: 1 to 1: 5 and is preferably in the range of 2: 1 to 1: 2.
Segun el procedimiento segun la invencion, se obtienen productos de papel, los cuales frente al procedimiento del estado de la tecnica presentan un nivel de resistencia en seco mas alto con al mismo tiempo resistencia en humedo baja. Estos papeles presentan, en comparacion con productos de papel conocidos, en particular un valor CMT alto.According to the process according to the invention, paper products are obtained, which in comparison with the prior art process have a higher dry resistance level with at the same time low wet resistance. These papers have, in comparison with known paper products, in particular a high CMT value.
Las partes indicadas en los siguientes ejemplos son partes de peso, las indicaciones de porcentaje se refieren al peso de los materiales. El valor K de los polfmeros se determino segun H. Fikentscher Cellulose-Chemie, volumen 13, 58 - 64 y 71 - 74 (1932) a una temperatura de 20 °C en 5 % en peso de soluciones salinas acuosas con un valor de pH de 7 y una concentracion de polfmero de 0,5 %. Significando en este caso K = k * 1000.The parts indicated in the following examples are parts of weight, the percentage indications refer to the weight of the materials. The K value of the polymers was determined according to H. Fikentscher Cellulose-Chemie, volume 13, 58-64 and 71-74 (1932) at a temperature of 20 ° C in 5% by weight of aqueous saline solutions with a pH value of 7 and a polymer concentration of 0.5%. Meaning in this case K = k * 1000.
Para las pruebas individuales se produjeron en pruebas de laboratorio hojas en un equipo de elaboracion de hojas de ensayo de laboratorio, segun metodo Rapid-Kothen. La longitud de desgarro en humedo se determino segun DINFor individual tests, sheets were produced in a laboratory test sheet making equipment, according to the Rapid-Kothen method. The tear length in wet was determined according to DIN
55
1010
15fifteen
20twenty
2525
3030
53 112, hoja 2. La determinacion del valor CMT se produjo segun DIN 53 143, la resistencia de compresion en corto (valor SCT) se midio segun DIN 54518 y la presion de rotura en seco segun DIN 53 141.53 112, sheet 2. The CMT value was determined according to DIN 53 143, the short compression resistance (SCT value) was measured according to DIN 54518 and the dry breaking pressure according to DIN 53 141.
EjemplosExamples
A partir de 100 % de papel residual mezclado se produjo en primer lugar una suspension de material acuosa del 4 %, la cual se diluyo entonces a una densidad de material de 0,4 %. El valor de pH de la suspension fue de 7,14, el grado del refinado tipo Schopper-Riegler 40° (°SR). La suspension de material contema 0,27 % de un agente antiespumante comercial (Afranil ® SLO). Se dividio entonces en 9 partes iguales, y segun el ejemplo de comparacion 1 o segun los ejemplos 1 a 8, se proceso en presencia de los polfmeros indicados en la tabla 1 en un equipo de elaboracion de hojas segun metodo Rapid-Kothen, dando lugar a hojas con una masa de superficie de 120 a 130 g/m2 Para poder comparar los resultados entre sf, se recalcularon los valores de medicion individuales a hojas con un peso por superficie de 120 g/m2. Los resultados obtenidos de esta manera se indican en la tabla 1.A suspension of 4% aqueous material was first produced from 100% mixed residual paper, which was then diluted to a material density of 0.4%. The pH value of the suspension was 7.14, the degree of the refined Schopper-Riegler type 40 ° (° SR). The suspension of material contains 0.27% of a commercial antifoaming agent (Afranil ® SLO). It was then divided into 9 equal parts, and according to comparison example 1 or according to examples 1 to 8, it was processed in the presence of the polymers indicated in table 1 in a sheet-making equipment according to the Rapid-Kothen method, giving rise to to sheets with a surface mass of 120 to 130 g / m2 In order to compare the results between sf, the individual measurement values to sheets with a surface weight of 120 g / m2 were recalculated. The results obtained in this way are indicated in table 1.
Ejemplo de comparacion 1Comparison Example 1
A partir de la suspension de material descrita arriba se conformo una hoja sin mas aditivos.From the suspension of material described above, a sheet with no more additives was formed.
Ejemplos 1 a 8Examples 1 to 8
Se usaron los siguientes polfmeros:The following polymers were used:
Como sulfonato de lignina se uso una solucion acuosa comercial de 54,69 % de la sal de calcio de acido lignosulfonico.A commercial aqueous solution of 54.69% of the calcium salt of lignosulfonic acid was used as lignin sulphonate.
PVAm 1: como polfmero cationico se uso un homopolfmero hidrolizado al 50 %, de N-vinilformamida en forma de una solucion acuosa del 13 %. El polfmero tema una masa molar Mw de 400 000.PVAm 1: A 50% hydrolyzed homopolymer of N-vinylformamide was used as a cationic polymer in the form of a 13% aqueous solution. The polymer has a molar mass Mw of 400,000.
Polfmero anionico 1: copolfmero a partir de 70 % de N-vinilformamida y 30 % de acrilato de sodio de masa molar MW de 400 000.Anionic polymer 1: copolymer from 70% N-vinylformamide and 30% sodium acrylate molar mass MW 400,000.
En los ejemplos 1 a 8 se dosificaron en respectivamente una prueba del material de papel descrito arriba en primer lugar las cantidades indicadas respectivamente en la tabla 1, de sulfonato de lignina, se mezclo la muestra, se anadio entonces tras un tiempo de espera de 20 segundos el polfmero cationico (PVAm 1), se mezclo nuevamente la muestra, se anadio tras un tiempo de espera de 20 segundos el polfmero anionico 1, se mezclo el material de papel obtenido de esta manera y se elimino el agua a continuacion en un equipo de elaboracion de hojas segun metodo Rapid-Kothen. Los valores convertidos a hojas con un peso de superficie de 120 g/m2 para la presion de rotura en seco, el valor SCT y el valor CMT se indican en la tabla 1.In Examples 1 to 8, a test of the paper material described above was first dosed respectively in the amounts indicated respectively in Table 1, of lignin sulphonate, the sample was mixed, then added after a waiting time of 20 seconds the cationic polymer (PVAm 1), the sample was mixed again, the anionic polymer 1 was added after a waiting time of 20 seconds, the paper material obtained was mixed in this way and the water was then removed in a set of elaboration of leaves according to the Rapid-Kothen method. Values converted to sheets with a surface weight of 120 g / m2 for dry break pressure, SCT value and CMT value are indicated in table 1.
Tabla 1Table 1
- Ejemplo de comparacion Comparison example
- 1 one
- Ejemplo Example
- 1 2 3 4 5 6 7 8 1 2 3 4 5 6 7 8
- Sulfonato de lignina [%] Lignin Sulfonate [%]
- - 0,5 1,0 1,5 1,0 2,0 3,0 0,5 1,0 - 0.5 1.0 1.5 1.0 2.0 3.0 0.5 1.0
- PVAm 1 [%] PVAm 1 [%]
- - 0,5 0,5 0,5 1,0 1,0 1,0 0,5 0,5 - 0.5 0.5 0.5 1.0 1.0 1.0 0.5 0.5
- Polfmero anionico [%] Anionic polymer [%]
- - - - - - - - 0,5 0,5 - - - - - - - 0.5 0.5
- Presion de rotura en seco [kPa] Dry burst pressure [kPa]
- 318,0 358,8 357,6 357,8 394,2 376,8 388,5 417,7 415,6 318.0 358.8 357.6 357.8 394.2 376.8 388.5 417.7 415.6
- Aumento [%] Increase [%]
- 0 13 12 13 24 18 22 31 31 0 13 12 13 24 18 22 31 31
- Valor SCT [kN/m] SCT value [kN / m]
- 1,88 2,09 2,11 2,09 2,22 2,36 2,21 2,48 2,42 1.88 2.09 2.11 2.09 2.22 2.36 2.21 2.48 2.42
- Aumento [%] Increase [%]
- 0 11 12 11 18 26 17 32 29 0 11 12 11 18 26 17 32 29
- Valor CMT [N] CMT value [N]
- 116,5 156,83 158,6 150,24 166,8 171,6 175,2 170,3 182,2 116.5 156.83 158.6 150.24 166.8 171.6 175.2 170.3 182.2
- Aumento [%] Increase [%]
- 0 35 36 29 43 47 50 46 56 0 35 36 29 43 47 50 46 56
Claims (13)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP06111267 | 2006-03-16 | ||
| EP06111267 | 2006-03-16 | ||
| PCT/EP2007/052238 WO2007104716A1 (en) | 2006-03-16 | 2007-03-09 | Method for producing paper, paperboard and cardboard having high dry strength |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| ES2625622T3 true ES2625622T3 (en) | 2017-07-20 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| ES07712497.2T Active ES2625622T3 (en) | 2006-03-16 | 2007-03-09 | Procedure for the manufacture of paper, cardboard and cardboard with high dry strength |
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| Country | Link |
|---|---|
| US (1) | US7922867B2 (en) |
| EP (1) | EP1999314B1 (en) |
| JP (1) | JP5156650B2 (en) |
| CN (1) | CN101405457B (en) |
| CA (1) | CA2644348C (en) |
| ES (1) | ES2625622T3 (en) |
| PT (1) | PT1999314T (en) |
| WO (1) | WO2007104716A1 (en) |
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|---|---|---|---|---|
| DE102004056551A1 (en) * | 2004-11-23 | 2006-05-24 | Basf Ag | Process for the production of paper, cardboard and cardboard with high dry strength |
| WO2009138457A1 (en) * | 2008-05-15 | 2009-11-19 | Basf Se | Method for producing paper, paperboard and cardboard with a high dry strength |
| EP2443284B2 (en) * | 2009-06-16 | 2020-11-18 | Basf Se | Method for increasing dry strength of paper, paperboard and cardboard |
| JP5571014B2 (en) * | 2011-02-21 | 2014-08-13 | Ｋｊ特殊紙株式会社 | Electromagnetic wave suppression sheet |
| TWI511999B (en) * | 2011-07-11 | 2015-12-11 | Ind Tech Res Inst | Electronic element, conductive polymer composition, and method for fabricating the same |
| US9388533B2 (en) | 2011-08-25 | 2016-07-12 | Solenis Technologies, L.P. | Method for increasing the advantages of strength aids in the production of paper and paperboard |
| US9908680B2 (en) | 2012-09-28 | 2018-03-06 | Kimberly-Clark Worldwide, Inc. | Tree-free fiber compositions and uses in containerboard packaging |
| US9816233B2 (en) | 2012-09-28 | 2017-11-14 | Kimberly-Clark Worldwide, Inc. | Hybrid fiber compositions and uses in containerboard packaging |
| US9562326B2 (en) * | 2013-03-14 | 2017-02-07 | Kemira Oyj | Compositions and methods of making paper products |
| CN104452455B (en) | 2013-09-12 | 2019-04-05 | 艺康美国股份有限公司 | The method that paper making auxiliary agent composition and increase are stayed at paper ash code insurance |
| CN104452463B (en) | 2013-09-12 | 2017-01-04 | 艺康美国股份有限公司 | Papermaking process and compositions |
| KR102485733B1 (en) * | 2014-03-28 | 2023-01-05 | 바스프 에스이 | Method for producing corrugated cardboard |
| CN106930142B (en) * | 2015-12-31 | 2020-03-24 | 艺康美国股份有限公司 | Dry strength agent composition and method for improving dry strength of paper |
| JP6999162B2 (en) * | 2017-12-22 | 2022-02-10 | 国立研究開発法人産業技術総合研究所 | Ion composite material containing lignin sulfonic acid and cationic polymer |
| US11098453B2 (en) | 2019-05-03 | 2021-08-24 | First Quality Tissue, Llc | Absorbent structures with high absorbency and low basis weight |
| WO2023031667A1 (en) * | 2021-08-30 | 2023-03-09 | Ecolab Usa Inc. | Use of modified lignin as a wet end strength additive |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US2721140A (en) * | 1952-09-19 | 1955-10-18 | Hercules Powder Co Ltd | Paper of high wet strength and process therefor |
| US3448005A (en) * | 1965-01-04 | 1969-06-03 | Weyerhaeuser Co | Process of forming wet strength paper containing a cationic resin and fumarated unsaturated oil |
| SE443818B (en) | 1978-04-24 | 1986-03-10 | Mitsubishi Chem Ind | PROCEDURE FOR MAKING PAPER WITH IMPROVED DRY STRENGTH |
| JPS57191394A (en) * | 1981-05-19 | 1982-11-25 | Rei Tech Inc | Papermaking method using lignin like substance and cationic polymer |
| DE3506832A1 (en) * | 1985-02-27 | 1986-08-28 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING PAPER WITH HIGH DRY RESISTANCE |
| DE3534273A1 (en) * | 1985-09-26 | 1987-04-02 | Basf Ag | METHOD FOR PRODUCING VINYLAMINE UNITS CONTAINING WATER-SOLUBLE COPOLYMERISATS AND THE USE THEREOF AS WET AND DRY-FASTENING AGENTS FOR PAPER |
| JPH01183598A (en) * | 1988-01-18 | 1989-07-21 | Showa Denko Kk | Production of paper and paperboard |
| KR0159921B1 (en) * | 1988-10-03 | 1999-01-15 | 마이클 비. 키한 | A composition comprising cathionic and anionic polymer process thereof |
| DE4001808A1 (en) | 1990-01-23 | 1991-07-25 | Basf Ag | Water sol co-polymer for water treatment - from unsatd. carboxylic acid and vinyl:amide deriv. |
| DE4241117A1 (en) * | 1992-12-07 | 1994-06-09 | Basf Ag | Use of hydrolyzed copolymers of N-vinylcarboxamides and monoethylenically unsaturated carboxylic acids in papermaking |
| US5630907A (en) | 1992-12-07 | 1997-05-20 | Basf Aktiengesellschaft | Use of hydrolyzed copolymers of N-vinylcarboxamides and monoethylenically unsaturated carboxylic acids in papermaking |
| JPH06184983A (en) * | 1992-12-21 | 1994-07-05 | Sumitomo Chem Co Ltd | Production of paper and paperboard |
| US6228217B1 (en) * | 1995-01-13 | 2001-05-08 | Hercules Incorporated | Strength of paper made from pulp containing surface active, carboxyl compounds |
| DE19530788C1 (en) * | 1995-08-22 | 1996-08-01 | Leica Ag | Measurement rod for geodetic measurements with bar coded measurement scale |
| DE19537088A1 (en) * | 1995-10-05 | 1997-04-10 | Basf Ag | Process for the production of dry and wet strength paper |
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| JP3151427B2 (en) * | 1997-11-06 | 2001-04-03 | 株式会社トキワ | Method for manufacturing corrugated cardboard |
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| US20040118540A1 (en) | 2002-12-20 | 2004-06-24 | Kimberly-Clark Worlwide, Inc. | Bicomponent strengtheninig system for paper |
| DE102004056551A1 (en) * | 2004-11-23 | 2006-05-24 | Basf Ag | Process for the production of paper, cardboard and cardboard with high dry strength |
-
2007
- 2007-03-09 JP JP2008558792A patent/JP5156650B2/en not_active Expired - Fee Related
- 2007-03-09 EP EP07712497.2A patent/EP1999314B1/en not_active Not-in-force
- 2007-03-09 US US12/282,358 patent/US7922867B2/en not_active Expired - Fee Related
- 2007-03-09 CN CN2007800092355A patent/CN101405457B/en not_active Expired - Fee Related
- 2007-03-09 CA CA2644348A patent/CA2644348C/en not_active Expired - Fee Related
- 2007-03-09 WO PCT/EP2007/052238 patent/WO2007104716A1/en active Application Filing
- 2007-03-09 ES ES07712497.2T patent/ES2625622T3/en active Active
- 2007-03-09 PT PT77124972T patent/PT1999314T/en unknown
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| Publication number | Publication date |
|---|---|
| WO2007104716A1 (en) | 2007-09-20 |
| CA2644348C (en) | 2014-06-10 |
| CA2644348A1 (en) | 2007-09-20 |
| JP2009530504A (en) | 2009-08-27 |
| CN101405457A (en) | 2009-04-08 |
| US7922867B2 (en) | 2011-04-12 |
| EP1999314A1 (en) | 2008-12-10 |
| CN101405457B (en) | 2011-08-17 |
| PT1999314T (en) | 2017-05-26 |
| US20100108279A1 (en) | 2010-05-06 |
| EP1999314B1 (en) | 2017-02-22 |
| JP5156650B2 (en) | 2013-03-06 |
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